CASE STUDY No 1.

ETHANOL - WATER SOLUTION SEPARATION

BY CONTINUOUS DISTILLATION
UNIVERSIDAD DE LA SABANA

Lucas Isaac Corredor Rojas; Sandra Daniela Motta Rodríguez

Separation operations and new technologies laboratory
February 19th, 2018

1. ABSTRACT

This experiment is reproduced in a distillation tower in order to determinate the changes

when a reflux is set and how pure is the distillation. Thus, some general calculation that
involved mass and energy balances over the tower distillation were made to predict the
equipment behavior, also some calibration need to be made during the laboratory to the
pumps and the refractometer to get precise an exact recollection data. Then the results are
going to be compered and analyzed based on the predicted calculations made and
simulation on Aspen Plus.

2. GENERAL PURPOSE: Determine the changes generated on the equipment

according to the reflux rate that the distillation tower is operating.

Specifics:

- Determine the rate of energy consumption.

- Determine the concentration of the distillate.
- Fabricate a calibration curve for the refractometer of known ethanol / water
concentrations.
- Elaborate the representation of the tower in a McCabe-Thiele diagram.

3- INTRODUCTION

Distillation is one of the oldest and important method of separation. The most active time in
this area of research was around the 70s. However, today is a relevant area of research,
with a great reception in the industrial field as in the university [1]. At the industry, this is the
most commonly applied separation technologies. it is responsible for up 50% of both capital
and operating cost in industrial process [2].

It happens when we need the separation of a liquid mixture by partial vaporization thereof
[3]; The vaporized fraction condenses and recovers as a liquid. The oldest distillation method
is the one used to obtain alcoholic beverages. Thus, when heating a mixture containing
water and alcohol, the lighter components, in this case alcohol, are concentrated in the
distillate. The distillation columns, elements used to carry out this process, are the result of
technological evolution in which exactly the same is done only in a more efficient way:
through a series of stages there are stepped evaporations and condensations, coupled
together [1].

There are 3 types of distillation; Simple distillation can be used to separate a mixture of two
substances in which only one of them is volatile. The volatile component will be collected by
condensation of the vapor, while the compound does not volatile will remain in the distillation
flash.
If both components of a mixture are volatile the simple distillation will not achieve it’s
complete separation. To achieve this separation, both the residue and the distillate obtained
should be subjected to further distillation. The so-called distillation columns carry out this
process continuously. In a distillation column the steam is condensed and re-distilled many
times before leaving the column.

Normally, small fractions of distillate are collected, and the process is known as fractional
distillation. The distillation technique can be adapted to liquids with very high boiling points
elevated or that are unstable at the temperature of their boiling point. This modification is
called vacuum distillation [4].

In the distillation process is necessary to have into account that when the relative volatility
of the system decreases, distillation becomes more difficult (α = 1.0), because the liquid and
vapor will have the same composition. Also, it's necessary remember that in some mixes we
can found an azeotropic concentration, like the previously topic, liquid and vapor have the
same composition. [5].

4- EXPERIMENTATION

The first thing that developed during the practice was to measure the alcohol concentration
of the solution with which the reboiler was fed. By using the alcoholometer it was possible
to determine the initial concentration, which corresponded to 45% alcohol in the solution.
The alcohol meter is used to know the alcohol content in a solution; It consists of a closed
glass tube at both ends, an end that weighs a weight, and a calibration scale [6].
It was necessary to empty the reboiler, because the solution we needed was 15%. The
solution removed from the kettle was added to a storage bin and the reboiler 3/4 of the
volume was filled with the 15% alcohol solution which was already prepared and stored; In
addition, 4 liters of a solution containing 10% ethanol concentration were added to a feed
tank.
The computer was turned on and the computer software was opened in the mimetic diagram
to verify the temperatures at which the dishes and other equipment were located. There was
a waiting time for the boiling temperature of the solution (79-84 ° C) to be reached, in the
console, the power controller was 1.3 kW.
During the waiting period, the solutions of volumetric flasks of 10%, 30%, 50% and 75%
volume of alcohol were prepared.
Using a refractometer and the solutions the refractive index of each solution was measured
and an alcohol solution scale was built, this is an accurate optical instrument used to
measure the refractive index of translucent solids and liquids, allowing to identify
substances, verify its purity or analyze the percentage of dissolved solute [7]. Approximately
3 drops of solution were placed in the main prism, the plate was closed to prevent the entry
of light and finally the observation of the scale through the lens was possible.
Once the solution reached the temperature and equilibrium was observed in the column
(liquid boiling), the power control was changed to 0.5 kW and the first temperature and IR
samples were taken (a sample was extracted with a syringe) of each plate and then, it was
analyzed in the refractometer). It started with a reflux ratio of 1: 1 and after 10 minutes of
waiting to ensure stabilization, the next batch of temperatures and IR was taken. Then the
ratio was changed to 3: 1 and after 10 minutes the process of taking the sample with the
syringe and the refractometer analysis was repeated.
For the last variation, the same reflux ratio of 3: 1 was left, the power was increased to 0.7
kW and an alternative work methodology was used, where the column was fed with the
pump.
After taking the final samples, the console was turned off, the main tank was emptied in a
bucket and 5 minutes later, waiting for the decrease of the temperature of said solution, it
was passed to a feed tank, as was done at the beginning of the practice with the solution of
45% volume of ethanol. The feeding was determined by measuring the total volume change
over time. It took a time of 7 minutes and 40 seconds.
On the other hand, a simulation was carried out in ASPEN which is a software designed for
the construction and simulation of a process.

5- RESULTS

5.1 TEORICAL

It was defined a feed of F=30mL/min with a concentration in the most volatile of Z= 0,15
also a desire distillated of XD=0,77 and bottoms of XB=0,04 as a first closed calculation it
was made with a total reflux of 2, the obtained diagram of the tower is:

The need equation for resolving the mass balances of these tower are:
Ec. Number
General balance 𝐹= 𝐷+ 𝐵 (1)
By component 𝐹𝑧𝐷 = 𝑋𝐷 ∗ 𝐷 + 𝑋𝐵 ∗ 𝐵 (2)
𝐿𝑜
Ratio Reflux 𝑅= 𝐷
(3)

Solving for B in equation (2) and adding it in equation (1) we obtained

𝐹 ∗ 𝑍𝐷 𝑋𝐷 −1
𝐷= 𝐹− ∗ (1 − )
𝑋𝐵 𝑋𝐵
Replacing was obtained a value of D showed in the diagram, now once the value of D is
obtained, from equation 1, B can be found. Now to obtain the energy used in the reboiler
the following values are needed

The Enthalpies values are:

ℎ𝐷 ( 𝑋𝐷: 0,77) = 30 𝑘𝑐𝑎𝑙/𝑘𝑔
ℎ𝐵 (𝑋𝐷: 0,05) = 90 𝐾𝑐𝑎𝑙/𝑘𝑔
ℎ𝑓 (𝑍 = 0,15 20°𝐶) = 20 𝑘𝑐𝑎𝑙/𝑘𝑔
𝐻1(𝑦1 = 𝑥𝐷 = 0,77) = 340 𝑘𝑐𝑎𝑙/𝑘𝑔

The flow rates in mass rate are the following

mL 1,0E − 06 m3 789 kg kg
4,167 ∗ ∗ 3
= 3,29E − 03
min 1 mL 1m min
mL 1,0E − 06 m3 789 kg kg
25,832 ∗ ∗ 3
= 2,04E − 02
min 1 mL 1m min
mL 1,0E − 06 m3 789 kg kg
30 ∗ ∗ 3
= 2,37 − 02
min 1 mL 1m min

5.2 EXPERIMENTAL

The recollection of experimental data was made in batch mode which differs with the
theorical data in some ways that will be discuss later. The way to determinate the
concentration over the trays was a measurement of the refractive index, so it was
necessary to make a curve pattern with known concentration of ethanol versus the
refractive index.
The recollection of the data for the batch mode and a part were there was a feed entering
the distillation column are shown in the following table.

5.3 SIMULATION

The first simulation was made in order to compare the theorical versus aspen results. It
was used a column called "Distil" which uses the Edmister method, with a reflux of 2 and 8
trays. These is the figure and the respective data about the currents
The column also calculates the total reflux ratio in function of the theorical plates, these
date in made in order to obtain XD=0,77

𝐾𝑐𝑎𝑙
𝑄𝐶 = (1 + 𝑅) ∗ 𝐷 ∗ (ℎ𝐷 − 𝐻1) = −3,06 min (4)

𝐾𝑐𝑎𝑙
𝑄𝑅 = 𝐷ℎ𝐷 + 𝐵ℎ𝐵 − 𝑄𝑐 − 𝐹ℎ𝑓 4,5207 (5)
min
McCabe-Thiele method: it is used to obtain the number of theorical plates and it relates the
rectification, feed and the stripping section of the column. It used over and XY diagram of
equilibrium, in which are drew the tree operating lines.

𝑞
The slope of feed line: 𝑆𝑙𝑜𝑝𝑒 = 𝑞−1
(6)

𝐻1 −ℎ𝑓
The value of q is: 𝑞: 𝐻1 −ℎ𝑏
(7)

𝐿 𝐿
Top Operating Line: 𝑌= 𝑉
𝑥 + (1 − 𝑉) ∗ 𝑋𝐷 (8)

Replacing values to equation 4, 5 and 6

340 − 20 1,28 𝐿 𝑅 2
𝑞: = 1,28 𝑆𝑙𝑜𝑝𝑒 = = 4,57 = =
340 − 90 0,28 𝑉 1+𝑅 3

Drawing these lines in the x-y diagram and joining XB with the intercept between the top
operating line and the feed line is obtained the stripping operating line.

Graph 1: Determination of theorical trays with the McCabe-Thiele Method

𝑁° 𝑜𝑓 𝑎𝑐𝑡𝑢𝑎𝑙 𝑡𝑟𝑎𝑦𝑠
𝐸𝑓 = 𝑁° 𝑜𝑓 𝑡ℎ𝑒𝑜𝑟𝑖𝑐𝑎𝑙 𝑡𝑟𝑎𝑦𝑠*100%

8
𝐸𝑓 = ( ) ∗ 100% = 88.99%
9
The feed was determinate by measurement the total change of volume in time, it was 500
mL in 7 minutes 40 seconds (460 seconds) giving a total of 65,21 mL/min. Using the
equation showed in the graph X we can obtained the concentration of ethanol in each tray
the results are shown in the following table.

At the end of the experimentation the overall percentage of ethanol was 0f 96%.

6. ANALYSIS

First of all, there is an inverse relationship between the reflux ratio and the number of
theoretical stages, this can be appreciated in table 5 were by increasing the number of
theoretical trays the ratio reflux decreases. The reflux ratio and number of theoretical stages
can both be varied to achieve an optimum balance, as can be seen in the theoretical results,
the number of stages obtained was 9 for a reflux of 2 not close enough to the 2,78 in table
5, it is true that the simulation made by Aspen are complex, this is why there is a difference
between what was obtained and the simulation. For an existing column, the number of trays
used is fixed, hence higher distillate concentration (mole fraction XD) can only be obtained
by increasing the reflux ratio [8]
In the experimental results there was certain problems at the moment, because the last trays
(the closest to the reboiler) present some kind of flooding, this changed the accuracy of the
data collection, however we can appreciated in the Graph 5 the fact that during distillation,
substances separate based on their boiling points, the boiling point of the mixture varies as
vapor rises in a distillation column, due to changes in temperature and pressure, in the
moment of the experimentation the equipment showed how the temperature increase from
the bottom to the top the main reason why the temperatures decreases is that the vapor
over the trays is richer in the most volatile component, and this component has a lower
boiling point [9]. The graph 3 show this pattern in terms of concentration, in the tray 9 which
is the reboiler but can be count as one stage the concentration is 0,1 molar in ethanol (the
initial feed) but as the vapor star to increase from stage to stage until the number 5 there
are certain changes, from this point the overall concentration is almost the same for the four
cases of reflux. However there is a difference how it is performed the distillation in each one,
for the first case in total reflux of 0 the purification in ethanol is faster according to the blue
line, the reflux ratio of 1 showed a decrease in the purification during the first trays, finally
the ratio reflux of 3 showed a little more purification in the first trays, this is something that
makes no sense because in the first trays the concentration of ethanol is almost at the same,
there are certainly differences but with the method used cannot be appreciate clearly.

The variation with the feed incoming at the 4th tray which is the yellow line in graph 5 showed
a decrease in the concentration in the lower trays, this can be explained because the
average concentration in the reboiler is around 10 % and the feed has this same
concentration, while the vapor coming from the reboiler has a higher concentration, the feed
has a lower one, making them pass to the bottom. The conditions of the feed affects how
the distillation occurs, for example if the feed is a subcooled fluid the amount of liquid in the
stripping section will increase, if it is overheated vapor the amount of vapor in the rectification
section will increase and both cases the increase is the almost the same amount of the feed,
while if it is a mixture of vapor and liquid it will divide in the same relation that is entering
[10]. The previous analysis also explains the why the concentration increase, due to the
conditions of the lab, the temperature and pressure made the liquid subcooled.

Finally, the power need for the reboiler to operate with deterrents reflux was constant, in this
way the optimum reflux is the minimum that just allows the column to maintain both products
in specification (what we want), this is if the energy cost is too high, on the other hand if it is
cheap there is no optimum. [11]

6 CONCLUSIONS

- The temperature and heat duty increase as the vapor fraction increases; in order to
obtain a bigger fraction of vapor as a product stream there will be needed a greater
heat exchange, and the drum temperature will increase.

- If we have each and every time a greater composition of the more volatile
component in a system, there won't be required as much energy as it does with
lower feed compositions, the less volatile component will require more energy.

- A distillate of 96% of the most volatile component (alcohol-Ethanol) was obtained,

this through the variation of reflows and our engineering judgment for choose the
adequate operating conditions.
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